Nearly Identical but Not Isotypic: Influence of Lanthanide Contraction on Cs2NaLn(PS4)2 (Ln = La–Nd, Sm, and Gd–Ho)

The effect of lanthanide contraction often results in topological and symmetry changes in compounds with the same compositions as a function of lanthanide cation size. Here we report on the first example of a lanthanide thiophosphate exhibiting a change in the lanthanide cation environment without a...

Ausführliche Beschreibung

Gespeichert in:
Bibliographische Detailangaben
Veröffentlicht in:Inorganic chemistry 2020-02, Vol.59 (3), p.1905-1916
Hauptverfasser: Klepov, Vladislav V, Pace, Kristen A, Breton, Logan S, Kocevski, Vancho, Besmann, Theodore M, zur Loye, Hans-Conrad
Format: Artikel
Sprache:eng
Schlagworte:
Online-Zugang:Volltext
Tags: Tag hinzufügen
Keine Tags, Fügen Sie den ersten Tag hinzu!
Beschreibung
Zusammenfassung:The effect of lanthanide contraction often results in topological and symmetry changes in compounds with the same compositions as a function of lanthanide cation size. Here we report on the first example of a lanthanide thiophosphate exhibiting a change in the lanthanide cation environment without any topological or symmetry change. A series of new lanthanide thiophosphates with mixed alkali cations were obtained via a flux crystal growth technique using a CsI flux. The obtained compounds Cs2NaLn­(PS4)2 (Ln = La–Nd, Sm, and Gd–Ho) were grown as large single crystals (∼0.1–1 mm3) and characterized using single-crystal X-ray diffraction and magnetic susceptibility measurements. As we moved across the series, the structural studies revealed a change in the lanthanide coordination environment depending on the identity of the lanthanide. Although all compounds in the Cs2NaLn­(PS4)2 series crystallize in the same space group and have the same Wyckoff atom positions, a slight change in size between Sm3+ and Gd3+ causes a subtle change in coordination number from 9 (for Ln = La–Sm) to 8 (for Ln = Gd–Ho), resulting in two distinct but virtually identical structure types. Ab initio calculations were performed, and the observed experimental trend was corroborated computationally. Magnetic measurements performed on the Cs2NaLn­(PS4)2 (Ln = Ce, Pr, Nd, Gd, and Tb) compounds revealed paramagnetic behavior.
ISSN:0020-1669
1520-510X
DOI:10.1021/acs.inorgchem.9b03200